Silver halide photographic light-sensitive material

ABSTRACT

A silver halide light-sensitive material having a support and at least one silver halide emulsion is provided. The silver halide emulsion layer contains in combination at least one cyan coupler of Formula (I) and at least one cyan coupler of Formula (II).

.Iadd.This application is a continuation of application Ser. No.07/326,782 filed Mar. 21, 1989 now abandoned. .Iaddend.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a silver halide photographiclight-sensitive material, and more particularly to a silver halidephotographic light-sensitive material which contains a cyan couplerexcellent in the solubility as well as in the dispersion stability andwhich is capable of giving a satisfactorily color-reproducible andwell-preservable dye image.

The formation of a dye image by use of a silver halide colorphotographic light-sensitive material is generally carried out in themanner that an aromatic primary amine color developing agent itself,when reducing the light-exposed silver halide particles of a silverhalide color photographic light-sensitive material, is oxidized, and theoxidized product reacts with a coupler that is in advance contained inthe silver halide color photographic light-sensitive material to therebyform a dye. And as the coupler, because the color reproduction isusually carried out by the color subtractive process, three differentcouplers; i.e., yellow, magenta and cyan couplers are used.

These couplers each is normally dissolved in a substantiallywater-insoluble high-boiling organic solvent or at need together with anauxiliary solvent, and the resulting solution is then adder to a silverhalide emulsion.

Fundamental requirements for the nature of these couplers are that thecoupler shall:

have large solubility in high-boiling organic solvents,

have no satisfactory dispersibility and dispersion stability that thecoupler is hardly deposited,

be so excellent in the spectral absorption characteristics as well as inthe color tone that a clear dye image can be formed in a wide colorreproduction range, and

form a dye image which is highly resistant to light, heat and moisture.Especially, the cyan coupler should be improved on two points: one isthat it should have litte or no absorption in the wavelength regionother than its intrinsic spectral absorption wavelength region, and theother is that it should have higher resistance to light, heat andmoisture.

Those conventionally known cyan couplers include2,5-diacylaminophenol-type cyan couplers which are phenol compounds thesecond and fifth positions of which are substituted by acylaminoradicals, as described in, e.g., U.S. Pat. No. 2,985,826, JapanesePatent Publication Open to Public Inspection (hereinafter referred to asJapanese Patent O.P.I. Publication) Nos. 112038/1975, 109630/1978 and163537/1980. When such a 2,5-diacylaminophenol-type cyan coupler is usedin a silver halide light-sensitive material, because of its very smallsecondary adsorption in the spectral wavelength range of from 400 to 450nm, the light-sensitive material becomes better in the blue colorreproduction as well as in the color restoration (cyan dye loss inprevented), and further becomes better improved on the darkdiscoloration resistance such as the resistance to heat and moisture, sothat the light-sensitive material can be largely improved on the cyandye image. However, the use of a 2,5-diacylaminophenol-type cyan couplercan not sufficiently satisfy the foregoing fundamental naturerequirements because the coupler has the disadvantages that (1) itsspectral minimum density in the wavelength range of from 450 to 480 nmis so high and its lightness is so low that its color reproducible rangebecomes narrow, while its absorption in the wavelength range of from 500to 550 nm is so high that its green color reproduction becomes poor, (2)its resistance to light is insufficient, and (3) its solubility anddispersion ability are unsatisfactory.

It is therefore a first object of the present invention to provide asilver halide photographic light-sensitive material containing a cyancoupler which is excellent in the spectral absorption characteristic andcapable of forming a clear dye image with good color tone in a widecolor reproduction range.

It is a second object of the present invention to provide a silverhalide photographic light-sensitive material which is improved so as tohave well balanced resistances to light, heat and moisture, and capableof forming a well preservable dye image.

It is a third object of the present invention to provide a silver halidephotographic light-sensitive material containing a cyan coupler which isexcellent in the solubility, dispersibility and dispersion stability.

We have now found that the above objects of the present invention can beaccomplished by a silver halide photographic light-sensitive materialcomprising a support having thereon at least one silver halide emulsionlayer containing in combination at least one of those cyan couplershaving the following Formula [I] and at least one of those cyan couplershaving the following Formula [II], and thus we have completed thepresent invention. ##STR1## wherein R₁ represents an aryl radical, acycloalkyl radical or a heterocyclic radical; R₂ represents an alkylradical or a phenyl radical; R₃ is a hydrogen atom, a halogen atom, analkyl radical or an alkoxy radical; and Z₁ is hydrogen atom, a halogenatom, or a radical that can be split off by the reaction of the couplerwith the oxidized product of an aromatic primary amine-type colordeveloping agent. ##STR2## wherein R₄ is an alkyl radical (such asmethyl, ethyl, butyl, nonyl, etc.); R₅ is an alkyl radical (such asmethyl, ethyl, etc.); R₆ is a hydrogen atom, a halogen atom (such asfluorine, chlorine, bromine, etc.) or an alkyl radical (such as methyl,ethyl, etc.); and Z₂ is a hydrogen atom, a halogen atom, or a radicalthat can be split off by the reaction of the coupler with the oxidizedproduct of an aromatic primary amine-type color developing agent.

In the present invention, the aryl radical represented by R₁ of Formula.[.[I].]. .Iadd.I .Iaddend.includes, e.g., phenyl, naphthyl, andpreferably phenyl. The heterocyclic radical represented by R₁ includes,e.g., pyridyl, furan, etc. The cycloalkyl radical represented by R₁includes, e.g., cyclopropyl, cyclohexyl, etc. These radicals representedby R₁ are allowed to have a single or a plurality of substituents; forexample, those typical substituents introducible to the phenyl includehalogens (such as fluorine, chlorine, bromine, etc.), alkyl radicals(such as, e.g., methyl, ethyl, propyl, butyl, dodecyl, etc.), hydroxyradical, cyano radical, nitro radical, alkoxy radicals (such as, e.g.,methoxy, ethoxy, etc.), alkyl-sulfonamido radicals (such as, e.g.,methyl-sulfonamido, octyl-sulfonamido, etc.), aryl-sulfonamidoradicals.[.).]. .Iadd.(.Iaddend.such as, phenylsulfonamido,naphthylsufonamido, etc.), alkyl-sulfamoyl radicals (such as, e.g.,butyl-sulfamoyl, etc.), aryl-sulfamoyl radicals (such as, e.g.,phenyl-sulfamoyl, etc.), alkoxycarbonyl radicals (such as, e.g.,methyloxycarbonyl, etc.), aryloxycarbonyl radicals (such as, e.g.,phenyloxycarbonyl, etc.), aminosulfonamido radical, acylamino radicals,carbamoyl radical, sulfonyl radical, sulfinyl radical, sulfoxy radical,sulfo radical, aryloxy radicals, alkoxy radicals, carboxyl radical,alkyl-carbonyl radicals, aryl-carbonyl radicals, aminocarbonyl radical,and the like. Not less than two of these substituents may be introducedto the phenyl radical. The preferred radicals represented by R₁ includephenyl radical or .Iadd.phenyl radicals having a single or a pluralityof substituents (which are typified by .Iaddend.halogens,alkyl-sulfonamido radicals, aryl-sulfonamido radicals, alkyl-sufamoylradicals, aryl-sulfamoyl radicals, alkyl-sulfonyl radicals,aryl-sulfonyl radicals, alkyl-carbonyl radicals, aryl-carbonyl radicals,and .[.phenyl radicals having one or not less than two.]. cyano radicals.[.as substituents.]..Iadd.).Iaddend. .

The alkyl radical represented by R₂ includes those in the straight chainor branched chain form, such as methyl, ethyl, propyl, butyl, octyl, andthe like radicals.

The preferred cyan couplers having Formula .[.[I].]. .Iadd.I .Iaddend.inthe present invention include those compounds having the followingFormula .[.[III].]..Iadd.III.Iaddend.: ##STR3## wherein R₇ represents aphenyl radical which is allowed to have a single or a plurality ofsubstituents which are typified by a halogen atom (such as fluorine,chlorine, bromine, etc.), an alkyl radical (such as, e.g., methyl,ethyl, propyl, butyl, octyl, dodecyl, etc.), a hydroxy radical, a cyanoradical, a nitro radical, an alkoxy radical (such as, e.g., methoxy,ethoxy, etc.), an alkyl-sulfonamido radical (such as, e.g.,methyl-sulfonamido, octyl-sulfonamido, etc.), an aryl-sulfonamidoradical (such as, e.g., phenyl-sulfonamido, .[.napththyl-sulfonamido.]..Iadd.naphthyl-sulfonamido.Iaddend., etc.), an alkyl-sulfamoyl radical(such as, e.g., butyl-sulfamoyl, etc.), an aryl-sulfamoyl radical (suchas, e.g., phenyl-sulfamoyl, etc.), an alkyloxycarbonyl radical (such as,e.g., methyloxycarbonyl, etc.), an aryloxycarbonyl radical (such as,e.g., phenyloxycarbonyl, etc.), and the like. Not less than two of thesesubstituents may be introduced to the phenyl radical.

The preferred radical represented by R₇ is a phenyl radical .[.havingsuch one substituent or not less than two substituents as phenylradicals or.]. .Iadd.or phenyl radicals having a single or a pluralityof substituents (which are typified by .Iaddend.halogens (preferablyfluorine or bromine), alkyl-sulfonamido radicals (preferablyO-methyl-sulfonamido, p-octyl-sulfonamido, o-dodecyl-sulfonamido),aryl-sulfonamido radicals (preferably phenyl-sulfonamido),alkyl-sulfamoyl radicals (preferably butyl-sulfamoyl), aryl-sulfamoylradicals (preferably phenyl-sulfamoyl), alkyl radicals (preferablymethyl, trifluoromethyl), or alkoxy radicals (preferably methoxy,ethoxy).Iadd.).Iaddend..

R₈ is an alkyl or aryl radical. The alkyl radical or the aryl radical isallowed to have a single or a plurality of substituents which may betypified by halogens (such as, e.g., fluorine, chlorine, bromine, etc.),hydroxyl radical, carboxyl radical, alkyl radicals (such as, e.g.,methyl, .[.ethy.]. .Iadd.ethyl.Iaddend., propyl, butyl, octyl, dodecyl,etc.), aralkyl radicals, cyano radical, nitro radical, alkoxy radicals(such as e.g., methoxy, ethoxy, etc.), aryloxy radicals,alkyl-sulfonamido radicals (such as, e.g., methyl-sulfonamido,octyl-sulfonamido, etc.), aryl-sulfonamido radicals (such as, e.g.,phenyl-sulfonamido, naphthyl-sulfonamido, etc.), alkyl-sulfamoylradicals (such as, e.g., butyl-sulfamoyl, etc.), aryl-sulfamoyl radicals(such as, e.g., phenyl sulfamoyl, etc.), alkyloxycarbonyl radicals (suchas, e.g., methyloxycarbonyl, etc.), aryloxycarbonyl radicals (such ase.g., phenyloxycarbonyl, etc.), aminosulfonamido radicals (such as,e.g., dimethylaminosulfonamido, etc.) alkyl-sulfonyl radicals,aryl-sulfonyl radicals, alkyl-carbonyl radicals, aryl-carbonyl radicals,aminocarbonylamido radical, carbamoyl radical, sulfinyl radical, and thelike. Not less than two of these substituents may be introduced to thealkyl or aryl radical.

The preferred radical represented by R₈, when the n is equal to 0, is analkyl and, when the n is equal to more than 1, is an aryl. The furtherpreferred radical represented by R₈ is a phenyl radical having .[.suchone substituent or not less than two.]. substituents as, when the n isequal to 0, alkyl radicals having from 1 to 22 carbon atoms (preferablymethyl, ethyl, propyl, butyl, octyl, dodecyl) and, when the n is equalto one or more than 1, phenyl, or alkyl radicals (preferably t-butyl,t-amyl, octyl), alkyl-sulfonamido radicals (preferablybutyl-sulfonamido, octyl-sulfonamido, dodecyl-sulfonamido),aryl-sulfonamido radicals (preferably phenyl-sulfonamido),aminosulfonamido radicals (preferably dimethylaminosulfonamido), oralkyloxycarbonyl radicals (preferably methyloxycarbonyl,butyloxycarbonyl.Iadd.).Iaddend..

.Iadd.R₉ represents an alkylene radical. .Iaddend.R₉ represents astraight-chain or branched-chain alkylene having from 1 to 20 carbonatoms, and more preferably from 1 to 12 carbon atoms.

R₁₀ is a hydrogen atom or a halogen atom (fluorine, chlorine orbromine), and preferably a hydrogen atom.

n is 0 or .[.an.]. .Iadd.a .Iaddend.positive integer and preferably 0 to5, more preferably 0 to 1.

X is a divalent radical such as --O--, --CO--, --COO--, --OCO--, --SO₂NR'--, NR'SO₂ NR"--, --S--, --SO-- or --SO₂ -- wherein R' and R" each isa substituted or unsubstituted alkyl radical, and preferably --O--,--S--, --SO-- and --SO₂ --.

Z₃ is a hydrogen atom, a halogen atom, or a radical that can be splitoff by the reaction of the coupler with the oxidized product of anaromatic primary amine-type color developing agent, the radical beingpreferably a chlorine atom or a fluorine atom.

The following are typical examples of the cyan coupler having Formula.[.[I].]. .Iadd.I.Iaddend., but the present invention is not limitedthereto. ##STR4##

The cyan couplers having Formula [II] in the present invention are morepreferably those compounds having the following Formula [IV]: ##STR5##wherein R₁₁ and R₁₂ may be either the same or different from each otherand each is a hydrogen atom, an alkyl radical (such as, e.g., methyl,ethyl, propyl, butyl, amyl, octyl, dodecyl, etc.) or an alkoxy radical(such as, e.g., methoxy, ethoxy, etc.), provided that the sum of thecarbon atoms of R₁₁ and R₁₂ is from 8 to 16, and more preferably R₁₁ andR₁₂ each is a butyl or amyl radical; R₁₃ is a hydrogen atom or an alkylradical (such as, e.g., methyl, ethyl, propyl, butyl, octyl, etc.), andpreferably a hydrogen atom, ethyl or butyl radical; m is an integer ofup to 2; and Z₄ is a hydrogen atom, a halogen atom, or a radical thatcan be split off by the reaction of the coupler with the oxidizedproduct of an aromatic primary amine-type color developing agent.

In Formulas [I], [II], [III] and [IV], the radicals that can be splitoff by the reaction of these couplers with the oxidized product of thearomatic primary amine-type color developing agents represented by Z₁,Z₂, Z₃ and Z₄ are all known to those skilled in the art. Any of theseradicals changes the reactivity of the coupler or is split from thecoupler to fulfill its development-inhibiting, bleach-inhibiting andcolor-compensation functions to thereby advantageously act in thecoupler-containing layers or other layers of the silver halide colorphotographic light-sensitive material. Typical examples of such radicalsinclude, for example, alkoxy radicals, aryloxy radicals, arylazoradicals, thioether, carbamoyloxy radical, acyloxy radicals, imidoradical, sulfonamido radical, thiocyano radical or heterocyclic radicals(such as, e.g., oxazolyl, diazolyl, triazolyl, tetrazolyl, etc.), andthe like. The particularly preferred examples represented by Z are ahydrogen atom or a chlorine atom.

The following are typical examples of those cyan couplers having Formula[II], but the present invention is not limited thereto. ##STR6##

In the case of using in combination the cyan coupler having Formula [I]of the invention and the cyan coupler having Formula [II] of theinvention, there may be used at least one of these cyan couplers havingFormula [I] and at least one of these cyan couplers having Formula [II]in an arbitrary proportion in the combination thereof, but it isdesirable that of the total amount of the cyan couplers the cyan couplerhaving Formula [II] be used in the quantity so as to account for from 30to 90 mole%, and more preferably from 50 to 90 mole%.

The silver halide color photographic light-sensitive material of thepresent invention is allowed to be of any construction as long as itcomprises a support having thereon at least one silver halide emulsionlayer, and no particular restrictions are placed on the number of andthe coating order of silver halide emulsion layers andnon-light-sensitive layers. Typical examples of the light-sensitivematerial include color positive or negative films, color photographicprinting papers, color slides, and those light-sensitive materials forspecial use such as for graphic arts use, radiography use, andhigh-resolution applications, and the like, and particularly suitablefor use as color photographic printing papers. Most of the foregoingsilver halide emulsion layers and non-light-sensitive layers are usuallycomprised of hydrophilic binder-containing hydrophilic colloidal layers.As the hydrophilic binder, there may be preferably used gelatin orgelatin derivatives such as acylated gelatin, guanidylated gelatin,carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin, andthe like.

These cyan couplers having Formulas [I] and [II] (hereinafter referredto as the cyan coupler(s) of the present invention) may be incorporatedby the application of the method for use in ordinary cyan dye-formingcouplers thereto into silver halide emulsion layers, the layers beingcoated on a support, thereby forming a photographic element. Thephotographic element is allowed to be either a monochromatic element ormulticolor element. In the case of the multicolor element, the cyancoupler of the present invention is usually incorporated into thered-sensitive silver halide emulsion layer, but may be allowed in anonlight-sensitive emulsion layer or emulsion layer that is sensitive tothree-primary-color regions excluding the red. Each component unitcapable of forming a dye image in the present invention is a single orone of a plurality of emulsion layers, having sensitivity to each givenspectral region.

The cyan coupler of the present invention may be incorporated into anemulsion in accordance with any of conventionally known methods. Forexample, the cyan coupler is dissolved separately into such a singlehigh-boiling organic solvent as a phthalate (dibutyl phthalate, etc.), aphosphate (tricresyl phosphate, etc.) or a N,N-dialkyl-substituted amide(N,N-diethyl-laurylamide, etc.) and into such a single low-boilingorganic solvent as butyl acetate or butyl propionate, or dissolved into,if necessary, a mixture of the high-boiling and low-boiling organicsolvents. After that, the solution is mixed with an aqueous gelatinsolution containing a surfactant, and then emulsified to be dispersed byuse of a high-speed mixer, a colloid mill or a ultrasonic disperser. Theresulting dispersed liquid is subsequently added to a silver halide,whereby a silver halide emulsion for use in the present invention can beprepared.

The cyan coupler of the present invention may be added to the silverhalide emulsion usually within the quantity range of from about 0.05 toabout 2 moles per mole of silver halide, and preferably from 0.1 to 1mole per mole of silver halide.

In the case where the silver halide color photographic light-sensitivematerial of the present invention is a multicolor element, all thelayers including the above image forming component unit layers requiredfor the photographic element may be coated in various orders as is knownto those skilled in the art. The typical multicolor photographic elementis one that comprises a support having thereon a cyan dye image-formablecomponent unit consisting of at least one red-sensitive silver halideemulsion layer containing a cyan dye forming coupler (at least one ofthe cyan dye forming couplers is the cyan coupler of the presentinvention having Formula [I] and at least further one of the cyancouplers is the cyan coupler of the present invention having Formula[III]); a magenta dye image-formable component unit consisting of atleast one green-sensitive silver halide emulsion layer containing atleast one magenta dye forming coupler; and a yellow dye image-formablecomponent unit consisting of at least one blue-sensitive silver halideemulsion layer containing at least one yellow dye forming coupler.

The photographic element may have additional layers; suchnonlight-sensitive layers as filter layers, interlayers, a protectivelayer, an antihalation layer, a subbing layer, and the like.

As the yellow dye forming coupler usable in the present invention theremay be suitably used those compounds having the following Formula [V]:##STR7##

wherein R₁₄ represents an alkyl radical (such as, e.g., methyl, ethyl,propyl, butyl, etc.) or an aryl radical (such as, e.g., phenyl,p-methoxyphenyl, etc.); R₁₅ represents an aryl radical; and Y representsa hydrogen atom or a radical which can be split off during the course ofa color developing reaction).

Further, particularly preferred as the yellow coupler capable of forminga dye image in the present invention are those compounds having thefollowing Formula [VI]: ##STR8## wherein R₁₆ is a halogen atom, analkoxy radical or an aryloxy radical; R₁₇, R₁₈ and R₁₉ each is ahydrogen atom, a halogen atom, an alkyl radical, an alkenyl radical, analkoxy radical, an aryl radical, an aryloxy radical, a carbonyl radical,a sulfonyl radical, a carbonyl radical, an alkoxycarbonyl radical, acarbonyl radical, a sulfone radical, a sulfamyl radical, a sulfonamidoradical, an acylamido radical, an ureido radical or an amido radical;and Y is as defined previously.

These are as described in, for example, U.S. Pat. Nos. 2,778,658,2,875,057, 2,908,573, 3,227,155, 3,227,550, 3,253,924, ,265,506,3,277,155, 3,341,331, 3,369,895, 3,384,657, 3,408,194, 3,415,652,3,447,928, 3,551,155, 3,582,322, 3,725,072, 3,894,875, West German OLSPatent Nos. 1,547,868, 2,057,941, 2,162,899, 2,163,812, 2,213,461,2,219,917, 2,261,361, 2,263,875, Japanese Patent Examined PublicationNo. 13576/1974, Japanese Patent O.P.I. Publication Nos. 29432/1973,66834/1973, 10736/1974, 122335/1975, 28834/1975 and 132926/1975, and thelike.

As the magenta dye image forming coupler, there may be preferably usedthose couplers having the following Formula [VII]: ##STR9## wherein Aris an aryl radical; R₂₀ is a hydrogen atom, a halogen atom, an alkylradical or an alkoxy radical; R₂₁ is an alkyl radical, an amido radical,an imido radical, an N-alkylcarbamoyl radical, an N-alkyl-sulfamoylradical, an alkyloxycarbonyl radical, an acyloxy radical, a sulfonamidoradical, or an urethane radical; Y is as defined in Formula [V]; and Wis --NH--, --NHCO-- (wherein the N atom is bonded with the carbon atomof pyrazolone nucleus) or --NHCONH--.

These are as described in, e.g., U.S. Pat. Nos. 2,600,788, 3,061,432,3,062,653, 3,127,269, 3,311,476, 3,152,896, 3,419,391, 3,519,429,3,555,318, 3,684,514, 3,888,680, 3,907,571, 3,928,044, 3,930,861,3,930,866, 3,933,500, Japanese Patent O.P.I. Publication Nos.29639/1974, 111631/1974, 129538/1974, 13041/1975, 58922/1977,62454/1980, 118034/1980, 38043/1981, British Pat. No. 1,247,493, BelgianPat. Nos. 769,116 and 792,525, West German Pat. No. 2,156,111, JapanesePatent Examined Publication No. 60479/1971, and the like.

The following are typical examples of the yellow and magenta dye imageforming couplers which are suitably usable in the present invention, butthe present invention is not limited thereto.

Yellow Couplers

(Y-1)α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]-acetanilide.

(Y-2)α-benzoyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butylamido]-acetanilide.

(Y-3)α-fluoro-α-pivalyl-2-chloro-5-[α-(2,4-di-t-amylphenoxy)butylamido]-acetanilide.

(Y-4) α-pivalyl-α-stearoyloxy-4-sulfamoyl-acetanilide.

(Y-5)α-pivalyl-α-[4-(4-benzyloxyphenyl-sulfonyl)phenoxy]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butylamido]-acetanilide.

(Y-6)α-(2-methoxybenzoyl)-α-(4-acetoxyphenoxy)-4-chloro-2-(4-t-octylphenoxy)-acetanilide.

(Y-7)α-pivalyl-α-(3,3-dipropyl-2,4-dioxo-acetidin-1-yl)-2-chloro-5-[α-(dodecyloxycarbonyl)-ethoxycarbonyl]-acetanilide.

(Y-8)α-pivalyl-α-succinimido-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butylamido]-acetanilide.

(Y-9) α-pivalyl-α-(3-tetradecyl-1-succinimido)-acetanilide.

(Y-10) Dipotassiumα-(4-dodecyloxybenzoyl)-α-(3-methoxy-1-succinimido)-3,5-dicarboxyacetanilide.

(Y-11)α-pivalyl-α-phthalimido-2-chloro-5-[α-2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-12)α-2-furyl-60-phthalimido-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-13)α-3-[α-(2,4-di-t-amylphenoxy)-butylamido]-benzoyl-α-succinimido-2-methoxyacetanilide.

(Y-14)α-phthalimido-α-pivalyl-2-methoxy-4-[(N-methyl-N-octadecyl)-sulfamoyl]-acetanilide.

(Y-15)α-acetyl-α-succinimido-2-methoxy-4-[(N-methyl-N-octadecyl)-sulfamoyl]-acetanilide.

(Y-16)α-cyclobutyryl-α-(3-methyl-3-ethyl-1-succinimido)-2-chloro-5-[(2,5-di-t-amylphenoxy)acetamido]-acetanilide.

(Y-17) α-(3-octadecyl-1-succinimido)-α-propanoyl-acetanilide.

(Y-18)α-(2,6-di-oxo-3-n-propyl-piperidine-1-yl)-α-pivalyl-2-chloro-5-[α-(2,4-di-t-amylphenoxy)-butyl-carbamoyl]-acetanilide.

(Y-19)α-(1-benzyl-2,4-dioxo-imidazolidine-3-yl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-20)α-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazine-4-yl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]acetanilide.

(Y-21)α-(3,3-dimethyl-1-succinimido)-α-pivalyl-2-chloro-5-[α-(2,4-di-t-amylphenoxy)-butylamido]acetanilide.

(Y-22)α-[3-(p-chlorophenyl)-4,4-dimethyl-2,5-dioxo-1-imidazolyl]-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-23)α-pivalyl-α-(2,5-dioxo-1,3,4-triazine-1-yl)-2-methoxy-5-[.alpha.-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-24)α-(5-benzyl-2,4-dioxo-3-oxazoyl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-25)α-(5,5-dimethyl-2,4-dioxo-3-oxazoyl)-α-pivalyl-2-chloro-5-[.alpha.-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-26)α-(3,5-dioxo-4-oxadinyl)-α-pivalyl-2-chloro-5-γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-27)α-pivalyl-α-(2,4-dioxo-5-methyl-3-thiazolyl)-2-chloro-5-[.gamma.-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-28)α-[3-(2H)-pyridazone-2-yl]-α-pivalyl-2-chloro-5-[γ-2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-29)α-[4,5-dichloro-3(2H)-pyridazone-2-yl]-α-benzoyl-2-chloro-5-[.alpha.-(dodecyloxycarbonyl)-ethoxycarbonyl]-acetanilide.

(Y-30)α-(1-phenyl-tetrazole-5-oxy)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-acetanilide.

(Y-31) 4,4'-di-(acetacetamino)-3,3-dimethyl-diphenylmethane.

(Y-32) P,P'-di-(acetacetamino)-diphenyl-methane.

Magenta Couplers

(M-1)1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecyl-carbamoyl-anilino)-5-pyrazolone.

(M-2)1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecanamidoanilino)-5-pyrazolone.

(M-3)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-γ-(2,4-di-t-amylphenoxy)-butyl-carbamoyl]-anilino-5-pyrazolone.

(M-4)1-(2,4,6-trichlorophenyl)-4-chloro-3-[2-chloro-5-γ-(2,4-di-t-amylphenoxy)-butyl-carbamoyl]-anilino-5-pyrazolone.

(M-5)1-(2,4,6-trichlorophenyl)-4-diphenyl-methyl-3-[2-chloro-5-(γ-octadecenylsuccinimido)-propyl-sulfamoyl]-anilino-5-pyrazolone.

(M-6)1-(2,4,6-trichlorophenyl)-4-acetoxy-5-(2-chloro-5-tetradecaneamido)-anilino-5-pyrazolone.

(M-7)1-[γ-(3-pentadecylphenoxy)-butylamido]-phenyl-3-anilino-4-(1-phenyl-tetrazole-5-thio)-5-pyrazolone.

(M-8)1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimido)-anilino-5-pyrazolone.

(M-9)1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimido)-anilino-5-pyrazolone.

(M-10)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-(N-phenyl-N-octyl-carbamoyl)]-anilino-5-pyrazolone.

(M-11)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-(N-butyl-carbonyl)-pyrazinyl-carbonyl]-anilino-5-pyrazolone.

(M-12)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-(2,4-dicarboxy-5-phenyl-carbamoyl)-benzylamido]-anilino-5-pyrazolone.

(M-13)1-(2,4,6-trichlorophenyl)-3-(4-tetradecyl-thiomethylsuccinimido)-anilino-5-pyrazolone.

(M-14)1-(2,4,6-trichlorophenyl)-3-[2-chloro-4-(2-benzofurylcarboxyamido)]-anilino-5-pyrazolone.

(M-15)1-(2,4,6-trichlorophenyl)-3-{2-chloro-4-[γ-(2,2-dimethyl-6-octadecyl-7-hydroxy-chroman-4-yl)-propionamido]}-anilino-5-pyrazolone.

(M-16)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-(3-pentadecylphenyl)-phenylcarboamido]-anilino-5-pyrazolone.

(M-17)1-(2,4,6-trichlorophenyl)-3-{2-chloro-5-[2-(3-t-butyl-4-hydroxyphenoxy)-tetradecanamido]-anilino}-5-pyrazolone.

(M-18)1-(2,6-dichloro-4-methoxyphenyl)-3-(2-methyl-5-tetradecanamido)-anilino-5-pyrazolone.

(M-19)4,4'-benzylidene-bis-[1-(2,4,6-trichlorophenyl)-3-{2-chloro-4-[γ-(2,4-di-t-amylphenoxy)-butylamido]-anilino}-5-pyrazolone.

(M-20)4,4'-benzylidene-bis[1-(2,3,4,5,6-pentachlorophenyl-3-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butylamido]-anilino]-5-pyrazolone.

(M-21)4,4'-(2-chloro)-benzylidene-bis-[1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-dodecylsuccinimido)-anilino]-5-pyrazolone.

(M-22)4,4'-benzylidene-bis-[1-(2-chlorophenyl)-3-(2-methoxy-4-hexadecanamido)-anilino-5-pyrazolone].

(M-23)4,4'-methylene-bis[1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-dodecenylsuccinimido)-anilino-5-pyrazolone)].

(M-24)1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)-benzamido]-5-pyrazolone.

(M-25)3-ethoxy-1-4-[α-(3-pentadecenylphenoxy)-butylamido]-phenyl-5-pyrazolone.

(M-26)1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-{α-(3-t-butyl-4-hydroxy)-phenyl}-tetradecanamido]-anilino-5-pyrazolone.

(M-27) 1-(2,4,6-trichlorophenyl)-3,3-nitriloanilino-5-pyrazolone.

Any of these yellow dye forming couplers and magenta dye formingcouplers may be incorporated into a silver halide emulsion layer withinthe quantity range of from 0.05 to 2 moles per mole of silver halide.

For the support of the light-sensitive material of the presentinvention, any of those materials may be used such as, for example,baryta paper, polyethylene-coated paper, polypropylene-synthetic paper,a transparent support material provided with a reflective layer ormaterial, a glass plate, cellulose acetate, cellulose nitrate, polyesterfilm such as polyethylene terephthalate, polyamide film, polycarbonatefilm, polystyrene film, and the like. These support materials may bearbitrarily selected according to the purpose for which is used thesilver halide photographic light-sensitive material of the presentinvention.

The coating process for use in coating the silver halide emulsion layersand nonlight-sensitive layers of the light-sensitive material of thepresent invention includes such various processes as the dipping coatingprocess, air-doctor coating process, curtain coating process, hoppercoating process, and the like.

The silver halide used for the silver halide emulsion of the presentinvention includes those arbitrarily used for ordinary silver halideemulsions: silver bromide, silver chloride, silver iodobromide, silverchlorobromide, silver chloroidobromide, and the like. The particles ofthese silver halides are allowed to be either coarse-grained orfine-grained, and be of either wide or narrow particle-sizedistribution.

The crystal of these silver halide particles may be either regular ortwin, and those having an arbitrary proportion of its [100] face to[111] face can be used. Further the crystal structure of these silverhalide particles may be either homogeneous from the inside to theoutside thereof or heterogeneous between the inside and the outsidethereof. Furthermore, these silver halides may be either of the type offorming a latent image mainly on the surface of the particles thereof orof the type of forming it inside the particles thereof. In addition,these silver halides may be prepared by any of the neutral method,ammoniacal method and acid method, and silver halide particles producedby any of the simultaneous mixing method, sequential mixing method andconversion method may be applied.

The silver halide emulsion of the present invention can be chemicallysensitized by the single or combined use of sulfur sensitizers such as,e.g., aryl-thiocarbamide, thiourea, cystine, etc.; active or insertselenium sensitizers; reduction sensitizers such as, e.g., stannoussalts, polyamides, etc.; noble-metallic sensitizers including such goldsensitizers as sodium aurithiocyanate, potassium chloroaurate,2-aurosulfobenzothiazolemethyl chloride, etc., water-soluble-saltsensitizers such as of ruthenium, rhodium, iridium, etc., and ammoniumchloropalladate, potassium chloropalladate, sodium chloropalladite, andthe like.

Into the silver halide emulsion of the invention may be incorporatedvarious known photographic additives such as those described in, e.g.,Research Disclosure No. 17643, December 1978.

The silver halide emulsion of the invention, in order to be providedwith sensitivity to the necessary wavelength region for a red-sensitiveemulsion is spectrally sensitized by the addition thereto of anappropriately selected sensitizing dye. As the spectral sensitizer,various sensitizing dyes may be used singly or in combination.

Advantageously applicable spectral sensitizers to the invention includesuch typical cyanine dyes, merocyanine dyes, and complex cyanine dyes asdescribed in U.S. Pat. Nos. 2,269,234, 2,270,378, 2,442,710 and2,454,620.

Other additives may also be arbitrarily incorporated into the silverhalide emulsion layers and nonlight-sensitive layers of the silverhalide photographic light-sensitive material of the present invention,the additives including antifoggants, antistain agents, brighteningagents, antistatic agents, hardening agents, plasticizers, wettingagents, ultraviolet absorbing agents, and the like, as described inResearch Disclosure No. 17643.

The thus constructed silver halide photographic light-sensitive materialof the present invention, after being exposed to light, is thendeveloped by the color development process including variousphotographic processing procedures. The preferred color developer liquidusable in the invention is one that contains an aromatic primaryamine-type color developing agent as the principal component thereof,the color developing agent being typified by p-phenylenediamine-typecompounds including, for example, diethyl-p-phenylenediaminehydrochloride, monomethyl-p-phenylenediamine hydrochloride,dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluenehydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene,2-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate,4-(N-ethyl-N-β-methanesulfonamidoethylamino)-aniline,4-(N-ethyl-N-β-hydroxyethylamino)aniline,2-amino-5-(N-ethyl-β-methoxyethyl)aminotoluene, and the like.

These color developing agents may be used singly or in combination, orused together with hydroquinone or the like. Further, the colordeveloper liquid contains generally alkali agents such as sodiumhydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite or thelike, and may also contains various additives including such halogenatedalkaline metals as, e.g., potassium bromide, and development controlagents such as, e.g., hydrazinic acid, and the like.

The silver halide photographic light-sensitive material of the presentinvention may contain in the hydrophilic colloidal layers thereof theforegoing color developing agent as it is or in the form of theprecursor thereof. The color developing agent precursor is a compoundcapable of producing a color developing agent under an alkalinecondition, the precursor including aromatic aldehyde derivative-Schiff'sbase-type precursors, multivalent metallic ion complex precursors,phthalic acid imide derivative precursors, phosphoric acid imidederivative precursors, sugar-amine reaction product precursors andurethane-type precursors. These aromatic primary amine color developingagent precursors are as described in, e.g., U.S. Pat. Nos. 3,342,599,2,507,114, 2,695,234, 3,719,493, British Pat. No. 803,783, JapanesePatent O.P.I. Publication Nos. 135628/1978 and 79035/1979, and ResearchDisclosure Nos. 15,159, 12,146 and 13,924. Any of these aromatic primaryamine color developing agents or precursors thereof should be added in aquantity enough to obtain a sufficient color formation during thedevelopment process. The quantity largely differs according to the kindof the light-sensitive material used, but is used within the range offrom about 0.1 mole to 5 moles, and preferably from 0.5 mole to 3 molesper mole of light-sensitive silver halide. These color developing agentsor precursors may be used singly or in combination. Into thephotographic light-sensitive material may be incorporated any of theforegoing compounds in the form of a solution of it dissolved into anappropriate solvent such as water, methanol, ethanol, acetone or thelike, or in the form of a dispersed liquid of it with use of ahigh-boiling organic solvent such as dibutyl phthalate, dioctylphthalate, tricresyl phosphate or the like, or in the form of itimpregnated into a latex polymer as described in Research Disclosure No.14850.

The silver halide photographic light-sensitive material of the presentinvention, after color development, is usually subjected to a bleach-fixbath processing or to separate bleaching and fixing treatments and thenwashed in water. As the bleaching agent, there may be used manycompounds, among which multivalent metallic compounds such as ofiron(III), cobalt(III), tin(II), and the like, especially complex saltsof these metallic cations with organic acids, such as, for example,metallic complex salts, ferricyanates or dichromates ofethylenediamine-tetraacetic acid, nitrilotriacetic acid,aminopolycarboxylic acids such as N-hydroxyethylethylenediamine-diaceticacid, malonic acid, tartaric acid, malic acid, diglycolic acid,dithioglycolic acid, and the like, may be used singly or in combination.

According to the silver halide photographic light-sensitive material ofthe present invention, the solubility, dispersibility and dispersionstability of the cyan coupler of the invention contained in the silverhalide emulsion layer are so good that no such trouble as deposition ofthe coupler will occur. The cyan coupler is excellent in the spectralabsorbing characteristic as well as in the color tone and capable offorming a clear dye image in an extensive color reproduction range;particularly a cyan dye image having the maximum absorption in thewavelength range of form 640 to 660 nm and having little or noabsorption in the regions of from 400 to 450 nm, from 450 to 480 nm, andfrom 500 to 550 nm, so that the coupler produces very excellent blue andgreen color reproductions with very satisfactory lightness with notrouble at all. Besides, the formed dye image is also excellent in theresistance to light, heat and moisture as well as in its preservability.

The present invention will be illustrated further in detail in referenceto examples below, but embodiments of the present invention are notlimited thereto.

EXAMPLE 1

The cyan couplers of the invention given in Table 1 and the followingcomparative couplers were used and 10 g of each of these couplers wasadded to a mixture of 5 ml of dibutyl phthalate with 30 ml of ethylacetate, and completely dissolved by heating to 60° C. This solution wasmixed with 5 ml of an aqueous 10% solution of Alkanol B(alkyl-naphthalenesulfonate, manufactured by DuPont) and 200 ml of anaqueous 5% gelatin solution, and this mixture was emulsified by means ofa colloid mill to prepare a coupler-dispersed liquid. The thus dispersedliquids each was added to 500 g of a silver chlorobromide (containing 80mole% silver bromide) emulsion, and the resulting emulsion was coated ona polyethylene-coated paper support and then dried, whereby 13 differentmonochromatic photographic elements were prepared. These samples wereexposed through an optical wedge to light and subsequently processed inthe baths given below in accordance with the following steps:

    ______________________________________                                        Processing steps                                                                             Temperature  Time                                              ______________________________________                                              Color developing                                                                           30° C.                                                                              3 min. & 30 sec.                                    Bleach-fix   30° C.                                                                              1 min. & 30 sec.                                    Washing      30° C.                                                                              2 min.                                        ______________________________________                                    

Compositions of the respective processing liquids are as follows:

    ______________________________________                                        Composition of the color developer:                                               4-amino-3-methyl-N--ethyl-N--(β-methane-                                                            5.0    g                                           sulfonamidoethyl)-aniline sulfate                                             Benzyl alcohol             15.0   ml                                          Sodium hexametaphosphate   2.5    g                                           Anhydrous sodium sulfite   1.85   g                                           Sodium bromide             1.4    g                                           Potassium bromide          0.5    g                                           Borax                      39.1   g                                           Water to make 1 liter                                                         Use sodium hydroxide to adjust the pH to 10.3                             Composition of the bleach-fix bath:                                               Iron-ammonium ethylenediamine-tetraacetate                                                               61.0   g                                           Diammonium ethylenediamine-tetraacetate                                                                  5.0    g                                           Ammonium thiosulfate       124.5  g                                           Sodium metabisulfite       13.5   g                                           Anhydrous sodium sulfite   2.7    g                                           Water to make 1 liter                                                     ______________________________________                                    

The thus processed samples each was tested for the spectral reflectioncharacteristics and preservability thereof in the following manners:

Spectral reflection characteristics test:

(i) Reflection maximum wavelength (λmax): The wavelength at which thereflection density becomes maximum was tested by use of Hitachi ColorAnalyzer Model 607.

(ii) Reduction density (D): Reflection densities at the wavelengths λ of550 nm, 470 nm and 420 nm when the maximum density is 2.0 by use of thesame color analyzer as in (i).

(iii) Lightness (L*): Measurements were made in accordance with theJapanese Industrial Standard JIS Z 8729-1980.

Dye image stability tests:

(iv) Light stability: Each of the resulting dye images was exposed tothe light of 45,000 luxes of a xenon fadometer over a period of 150hours, and after that the residual density at the initial density of 1.0was measured.

(v) Dark stability: After storing the samples at 77° C. in the dark fortwo weeks, the residual density of each of the samples at the initialdensity of 1.0 was measured.

The results obtained in (i)-(v) are given together in Table 1. ##STR10##

    __________________________________________________________________________    Cyan coupler compositions                                                     Exemplified                                                                              Exemplified                                                                          Comparative                                                                          Spectral reflection density                          couplers of                                                                              couplers of                                                                          Cyan cou - D           Dye image stability                  Sample                                                                            Formula (I)                                                                          Formula (II)                                                                         plers and  λ =                                                                       λ =                                                                       λ =                                                                          Light                                                                              Dark                            No. and mole %                                                                           and mole %                                                                           mole % λmax                                                                       550                                                                              470                                                                              420                                                                              L* stability                                                                          stability                       __________________________________________________________________________    1   I-5, 100                                                                              --    --     650 1.22                                                                             0.38                                                                             0.74                                                                             39.3                                                                             0.79 0.98 Comparative                                                                   Invention                  2   I-5, 80                                                                              II-3, 20                                                                             --     650 1.04                                                                             0.29                                                                             0.78                                                                             43.5                                                                             0.87 0.97 Comparative                                                                   Invention                  3   I-5, 60                                                                              II-3, 40                                                                             --     650 1.01                                                                             0.28                                                                             0.80                                                                             44.4                                                                             0.91 0.95 Comparative                                                                   Invention                  4   I-5, 80                                                                              II-1, 20                                                                             --     650 1.03                                                                             0.29                                                                             0.79                                                                             43.7                                                                             0.88 0.96 Comparative                                                                   Invention                  5   I-37, 100                                                                             --    --     655 1.15                                                                             0.43                                                                             0.76                                                                             37.6                                                                             0.38 0.99 Comparative                                                                   Invention                  6   I-37, 80                                                                             II-3, 20                                                                             --     653 1.02                                                                             0.31                                                                             0.80                                                                             42.0                                                                             0.77 0.97 Comparative                                                                   Invention                  7   I-4, 100                                                                              --    --     640 1.31                                                                             0.39                                                                             0.74                                                                             37.0                                                                             0.61 0.98 Comparative                                                                   Invention                  8   I-4, 60                                                                              II-3, 40                                                                             --     647 1.08                                                                             0.30                                                                             0.78                                                                             42.3                                                                             0.84 0.97 Comparative                                                                   Invention                  9    --    II-3, 100                                                                            --     650 1.02                                                                             0.27                                                                             0.94                                                                             45.0                                                                             0.91 0.64 Comparative                                                                   Invention                  10   --    II-1, 100                                                                            --     650 1.02                                                                             0.27                                                                             0.94                                                                             45.2                                                                             0.92 0.65 Comparative                                                                   Invention                  11   --     --    C-1, 100                                                                             647 1.05                                                                             0.35                                                                             0.97                                                                             38.4                                                                             0.71 0.63 Comparative                                                                   Invention                  12  I-5, 60                                                                               --    C-1, 40                                                                              649 1.04                                                                             0.35                                                                             0.98                                                                             38.5                                                                             0.72 0.87 Comparative                                                                   Invention                  13   --     --    C-2, 100                                                                             644 1.11                                                                             0.35                                                                             0.95                                                                             37.2                                                                             0.73 0.59 Comparative                                                                   Invention                  14  I-5, 60                                                                               --    C-2, 40                                                                              648 1.07                                                                             0.36                                                                             0.94                                                                             37.6                                                                             0.73 0.87 Comparative                                                                   Invention                  15   --     --    C-3, 100                                                                             700 0.90                                                                             0.33                                                                             0.88                                                                             39.4                                                                             0.42 0.81 Comparative                                                                   Invention                  16  I-5, 60                                                                               --    C-3, 40                                                                              667 1.01                                                                             0.35                                                                             0.85                                                                             39.2                                                                             0.51 0.88 Comparative                                                                   Invention                  __________________________________________________________________________

As apparent from the results shown in Table 1, the silver halide colorphotographic light-sensitive material samples of the present inventionhave little undesirable absorptions in 550 nm and 420 nm and lowreflection minimum densities as compared to the silver halide colorphotographic light-sensitive material samples containing compoundshaving Formula [I] alone, thus resulting in the formation of a dye imagehaving a high lightness and satisfactory spectral reflectioncharacteristics. This is quite an unexpected multiplied effect obtaineddue to the use of the cyan couplers having Formula [II]. And the formeddye image displays very satisfactory results in respect of theresistance to light and dark stability.

EXAMPLE 2

The cyan couplers of the present invention and the comparative couplersshown in Table 1 were used, and 0.1 mole of each of the couplers wasadded to and dissolved by heating to 60° C. into a mixture liquid of 20ml of dibutyl phthalate and ethyl acetate. The necessary quantity of theethyl acetate for the dissolution was measured. The results are as shownin Table 2. The thus obtained coupler solutions each was then mixed withthe same aqueous Alkanol B solution as in Example 1 and an aqueousgelatin solution, and the mixture was emulsified by means of a colloidmill to thereby prepare a coupler-dispersed liquid. Thecoupler-dispersed liquid was subsequently added to 1000 ml of ared-sensitive silver chlorobromide emulsion (containing 70 mole% ofsilver bromide) containing photographic additives such as a hardeningagent, coating aid, and the like, whereby a coating liquid for making ared-sensitive emulsion layer. These coupler-dispersed liquid-containingsilver halide emulsion coating liquids each, being kept at a temperatureof 40° C., was flowed at a rate of 2 liters per minute for 48 hoursthrough stainless tubing with its internal diameter of 5 cm by use of acirculation pump, and the time of a deposit beginning to attach to theinside wall of the tubing and the attached quantity of the deposit twodays later were measured. The obtained results are as given in Table 2.As apparent from the results shown in Table 2, the cyan couplers of thepresent invention are very excellent in the solubility, dispersibilityand dispersion stability.

                                      TABLE 2                                     __________________________________________________________________________    Cyan coupler composition                                                          Exemplified                                                                          Exemplified                                                                          Comparative                                                                          Necessary quan-                                          couplers of                                                                          couplers of                                                                          cyan cou-                                                                            tity of ethyl    Quantity of                         Sample                                                                            Formula (I)                                                                          Formula (II)                                                                         plers and                                                                            acetate for dis-                                                                       Time of begin-                                                                        deposition                          No. and mole %                                                                           and mole %                                                                           mole % solution (ml)                                                                          ning deposition                                                                       (mg/1000 m.sup.2)                   __________________________________________________________________________    15  I-5, 100                                                                              --    --     170       3 hrs later                                                                          1540   Comparative                                                                   Invention                    16  I-5, 80                                                                              II-3, 20                                                                             --     110      16 hrs later                                                                           210   Comparative                                                                   Invention                    17  I-5, 60                                                                              II-3, 40                                                                             --     100      18 hrs later                                                                           180   Comparative                                                                   Invention                    18  I-5, 80                                                                              II-1, 20                                                                             --     100      17 hrs later                                                                           190   Comparative                                                                   Invention                    19  I-37, 100                                                                             --    --     160       4 hrs later                                                                          1420   Comparative                                                                   Invention                    20  I-37, 80                                                                             II-3, 20                                                                             --     120      17 hrs later                                                                           190   Comparative                                                                   Invention                    21  I-4, 100                                                                              --    --     150       2 hrs later                                                                          1660   Comparative                                                                   Invention                    22  I-4, 60                                                                              II-3, 40                                                                             --     100      15 hrs later                                                                           220   Comparative                                                                   Invention                    23   --    II-3, 100                                                                            --     100      18 hrs later                                                                           190   Comparative                                                                   Invention                    24   --    II-1, 100                                                                            --      90      17 hrs later                                                                           180   Comparative                                                                   Invention                    25   --     --    C-1, 100                                                                              80      20 hrs later                                                                           120   Comparative                                                                   Invention                    26  I-5, 60                                                                               --    C-1, 40                                                                              150       5 hrs later                                                                          1370   Comparative                                                                   Invention                    27   --     --    C-2, 100                                                                              90      19 hrs later                                                                           190   Comparative                                                                   Invention                    28  I-5, 60                                                                               --    C-2, 40                                                                              160       7 hrs later                                                                          1460   Comparative                                                                   Invention                    __________________________________________________________________________

EXAMPLE 3

The following layers were coated on a polyethylene-coated paper supportin the described order from the support side to thereby preparemulticolor photographic element samples.

First layer:

An yellow coupler-containing blue sensitive silver halide emulsion (asilver chlorobromide emulsion containing 90 mole% of silver bromide and300 g of gelatin per mole of silver halide and also containing 0.5 moleper mole of silver halide of an yellow coupler YC-1 dissolved intodibutyl phthalate and dispersed into the emulsion) is coated so that thecoating quantity of gelatin is 2 g/m², and then dried.

Second layer:

A first interlayer (a gelatin layer of 1.5 g of gelatin/m²).

Third layer:

A magenta coupler-containing green-sensitive silver halide emulsion (asilver chlorobromide emulsion containing 80 mole% of silver bromide and400 g of gelatin per mole of silver halide and also containing 0.3 moleper mole of silver halide of the following magenta couple MC-1 dissolvedinto dibutyl phthalate and dispersed into the emulsion) is coated sothat the coating quantity of gelatin is 2 g/m², and then dried.

Fourth layer:

An ultraviolet absorbing agent-containing second interlayer (containingthe following ultraviolet absorbing agent UV-1: a solution of the agentdissolved into 20 g of dibutyl phthalate is dispersed into gelatin, andthe dispersed liquid is coated so that the coating quantity of the agentis 0.6 g/m² and that of gelatin is 1.5 g/m², and then dried.).

Fifth layer:

Cyan coupler-containing red-sensitive silver halide emulsions [silverchlorobromide emulsion containing 80 mole% of silver bromide and 300 gof gelatin per mole of silver halide] into parts of which emulsions aredispersed separately dibutyl phthalate solutions of the cyan couplers ofthe invention Ex emplified couplers having Formula [I] and [II],respectively, and into the other parts of which emulsion are dispersedseparately the same comparative couplers-1 or -2 as in Example 1,respectively, (the individual quantities of the respective couplers aregiven in mole% to the total amount of all the cyan couplers in Table 3),the emulsions containing 0.4 mole per mole of silver halide of the abovecouplers, respectively) each is coated so that the coating quantity ofgelatin is 20 g/m², and then dried.

Sixth layer:

A protective layer (a gelatin layer of 1.5 g of gelatin/m²).

The thus prepared samples 29-42 each was exposed to blue, green, and redlights through a wedge by use of a sensitometer (Model KS-7,manufactured by Konishiroku Photo Ind. Co., Ltd.), and then processed inthe following baths in accordance with the processing steps given below:

    ______________________________________                                        Processing steps (32.8° C.)                                                                     Processing time                                          Color developing         3 min. & 30 sec.                                     Bleach-fix               1 min. & 30 sec.                                     Washing                  3 min. & 30 sec.                                     Drying                                                                    Composition of the color developer:                                               N--ethyl-N--β-methanesulfonamidoethyl-                                                            4.0     g                                            3-methyl-4-aminoaniline sulfate                                               Hydroxyamine sulfate     2.0     g                                            Potassium carbonate      25.0    g                                            Sodium chloride          0.1     g                                            Sodium bromide           0.2     g                                            Anhydrous sodium sulfate 2.0     g                                            Benzyl alcohol           10.0    ml                                           Polyethylene glycol (average polymeriza-                                                               3.0     ml                                           tion degree: 400)                                                             Water to make 1 liter                                                         Use sodium hydroxide to adjust the pH to 10.0.                            Composition of the bleach-fix bath:                                               Iron-ammonium ethylenediamine-tetra-                                                                   60.0    g                                            acetate                                                                       Ammonium thiosulfate     100.0   g                                            Sodium hydrogensulfate   20.0    g                                            Sodium metabisulfite     5.0     g                                            Water to make 1 liter                                                         Use sulfuric acid to adjust the pH to 7.0                                 ______________________________________                                         ##STR11##

The thus processed samples were tested for the evaluation of thecolor-reproducible region thereof and for the dye image preservabilitythereof.

Color-reproducible region evaluation tests:

In accordance with the method for representing colors by the L*, u* andv* systems specified by the Japanese Industrial Standard JIS Z8729-1980, a chromaticity diagram of u' and v', when L* is equal to 50,was prepared for each of the samples to thereby evaluate thecolor-reproducible region (as integrated value) from the relative areasformed by the yellow, magent and cyan dyes. Further, the color areaformed by the formed cyan and magenta dyes was regarded as theblue-reproduced region, the color area formed by the formed cyan andyellow dyes as the green-reproduced region, and the color area formed bythe formed magenta and yellow dyes as the red-reproduced region, andthese respective color-reproduced regions were evaluated from therelative areas thereof.

Image preservability tests:

The formed yellow (Y), magenta (M) and cyan (C) dye images were testedfor the light stability and the dark stability in the same manners as inExample 1.

The results obtained from the above tests are as given together in Table3.

                                      TABLE 3                                     __________________________________________________________________________    Cyan coupler composition                                                         Exemplified                                                                          Exemplified                                                                          Comparative                                                                          Color-reproducible                                    Sam-                                                                             couplers of                                                                          couplers of                                                                          cyan cou-                                                                            region                                                ple                                                                              Formula (I)                                                                          Formula (II)                                                                         plers and                                                                            over-         Light stability                                                                        Dark stability                 No.                                                                              and mole %                                                                           and mole %                                                                           mole % all blue                                                                             green                                                                             red                                                                              C  M  Y  C  M  Y                        __________________________________________________________________________    29 I-5, 100                                                                              --    --     102 122                                                                              84  100                                                                              0.77                                                                             0.89                                                                             0.88                                                                             0.98                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             30 I-5, 80                                                                              II-3, 20                                                                             --     112 121                                                                              98  100                                                                              0.87                                                                             0.88                                                                             0.88                                                                             0.97                                                                             0.98                                                                             0.97                                                                             Comparative                                                                   Invention             31 I-5, 60                                                                              II-3, 40                                                                             --     114 120                                                                              99  100                                                                              0.90                                                                             0.90                                                                             0.87                                                                             0.95                                                                             0.99                                                                             0.97                                                                             Comparative                                                                   Invention             32 I-5, 80                                                                              II-1, 20                                                                             --     112 121                                                                              98  100                                                                              0.89                                                                             0.89                                                                             0.88                                                                             0.96                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             33 I-37, 100                                                                             --    --      95 118                                                                              83  100                                                                              0.40                                                                             0.88                                                                             0.87                                                                             0.99                                                                             0.98                                                                             0.98                                                                             Comparative                                                                   Invention             34 I-37, 80                                                                             II-3, 20                                                                             --     109 117                                                                              99  100                                                                              0.80                                                                             0.90                                                                             0.88                                                                             0.97                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             35 I-4, 100                                                                              --    --      99 120                                                                              85  100                                                                              0.62                                                                             0.89                                                                             0.89                                                                             0.98                                                                             0.99                                                                             0.97                                                                             Comparative                                                                   Invention             36 I-4, 60                                                                              II-3, 40                                                                             --     111 119                                                                              100 100                                                                              0.85                                                                             0.90                                                                             0.89                                                                             0.97                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             37  --    II-3, 100                                                                            --     100 100                                                                              100 100                                                                              0.90                                                                             0.91                                                                             0.88                                                                             0.64                                                                             0.98                                                                             0.97                                                                             Comparative                                                                   Invention             38  --    II-1, 100                                                                            --     100 100                                                                              100 100                                                                              0.90                                                                             0.90                                                                             0.88                                                                             0.65                                                                             0.98                                                                             0.97                                                                             Comparative                                                                   Invention             39  --     --    C-1, 100                                                                              92  95                                                                              91  100                                                                              0.71                                                                             0.88                                                                             0.88                                                                             0.62                                                                             0.99                                                                             0.99                                                                             Comparative                                                                   Invention             40 I-5, 60                                                                               --    C-1, 40                                                                               93  97                                                                              87  100                                                                              0.71                                                                             0.88                                                                             0.88                                                                             0.84                                                                             0.98                                                                             0.97                                                                             Comparative                                                                   Invention             41  --     --    C-2, 100                                                                              90  95                                                                              90  100                                                                              0.74                                                                             0.88                                                                             0.89                                                                             0.60                                                                             0.98                                                                             0.98                                                                             Comparative                                                                   Invention             42 I-5, 60                                                                               --    C-2, 40                                                                               92  98                                                                              86  100                                                                              0.73                                                                             0.88                                                                             0.89                                                                             0.86                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             43  --     --    C-3, 100                                                                              91  96                                                                              91  100                                                                              0.44                                                                             0.85                                                                             0.88                                                                             0.81                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             44 I-5, 60                                                                               --    C-3, 40                                                                               93 103                                                                              84  100                                                                              0.52                                                                             0.86                                                                             0.87                                                                             0.88                                                                             0.99                                                                             0.98                                                                             Comparative                                                                   Invention             __________________________________________________________________________

As apparent from Table 3, the multicolor photographic elements which usethe cyan couplers of the present invention show much improved blue colorreproductions with clear dye images formed in a wide color reproductionregion without any adverse effect on the green color reproduction, andfurther show well-balanced degree of cyan-magenta-yellow discoloration,thus showing much improved dye image stability on the whole.

EXAMPLE 4

Monochromatic photographic element samples were prepared in the samemanners as in previous examples with the exception that ExemplifiedCouplers I-16, I-36, I-33, II-4 and II-5 were used in place of the I-5,I-37, I-4, II-3 and II-1, respectively, and Comparative Couplers-4, -5and -6 in place of the Comparative Couplers-1, -2 and -3.

The thus obtained 14 different samples were used for the same tests asin Example 1. As a result, the silver halide color photographiclight-sensitive material samples of the present invention have lessundesirable absorptions in 550 nm and 420 nm and lower reflectionminimum densities than do the silver halide color photographiclight-sensitive material samples containing those of Formula [I] alone,so that the samples of the present invention form high lightness andsatisfactory spectral reflection characteristics--having dye images. Andthe formed dye images display very satisfactory light stability and darkstability characteristics. ##STR12##

EXAMPLE 5

Similar multicolor photographic element samples to the multicolorphotographic element samples of Example 3 were prepared in the samemanners as in Example 3 with the exception that the exemplified couplerswere replaced by those used in Example 4, respectively, and the YC-1,MC-1 and UV-1 were replaced by the following YC-2, MC-2 and UV-2,respectively.

The thus obtained 14 different samples were subjected to the same testsas in Example 3. As a result, the cyan couplers of the presentinvention--used multicolor photographic element samples show improvedred, green and blue color reproductions, particularly the conspicuousimprovement on the blue-color reproduction, with clear dye image formedin a wide color reproduction region, and also show well-balanced degreeof cyan-magenta-yellow discoloration, thus showing much improved imagepreservability on the whole.

What is claimed is:
 1. A silver halide photographic light-sensitivematerial comprising a support having thereon at least one silver halideemulsion layer containing in combination at least one of those cyancouplers having the following Formula [I] and at least one of those cyancouplers having the following Formula [II]:wherein R₁ is an arylradical, a cycloalkyl radical or a heterocyclic radical; R₂ is an alkylradical, a phenyl radical, or R₈ --X-R₉ --_(n) wherein R₈ represents analkyl or aryl radical, R₉ represents an alkylene radical, n representsan integer of 0 to 5, and X represents a divalent radical selected fromthe group consisting of --O--, --CO--, --COO--, --OCO--, --SO₂ NR'--,--NR'SO₂ NR"--, --S--, --SO-- and --SO₂ --, wherein R' and R" representan alkyl radical; R₃ is a hydrogen atom, a halogen atom, an alkylradical or an alkoxy radical; and Z₁ is a hydrogen atom, a halogen atom,or a radical that can be split off by the reaction of said coupler withthe oxidized product of an aromatic primary amine-type color developingagent, ##STR14## wherein R₄ is an alkyl radical or ##STR15## wherein R₁₁and R₁₂ may be either the same or different from each other and each isa hydrogen atom, an alkyl radical or an alkoxy radical, provided thatthe sum of the carbon atoms or R₁₁ and R₁₂ is from 8 to 16, R₁₃ is ahydrogen atom or an alkyl radical, and m is an integer of 0 to 2; R₅ isan alkyl radical; R₆ is a hydrogen atom, a halogen atom, or an alkylradical; and Z₂ is a hydrogen atom, a halogen atom, or a radical thatcan be split off by the reaction of said coupler with the oxidizedproduct of an aromatic primary amine-type color developing agent.Iadd.,wherein said silver halide emulsion layer does not contain an aromaticprimary amine-type color developing agent or a precursorthereof.Iaddend..
 2. The light-sensitive material of claim 1, whereinthe aryl radical represented by R₁ in Formula [I] is a phenyl radical.3. The light-sensitive material of claim 1, wherein the cyan couplershaving Formula [I] are those compounds having the following formula[III]: ##STR16## wherein R₇ represents a phenyl radical, R₈ representsan alkyl or aryl radical, R₉ represents an alkylene radical, R₁₀represents a hydrogen atom or a halogen atom, n represents an integer of0 to 5, X represents a divalent radical selected from the groupconsisting of --O--, --CO--, --COO--, --OCO--, --SO₂ NR'--, --NR'SO₂NR"--, --S--, --SO-- and --SO₂ -- wherein R' and R" represent an alkylradical and Z₃ represents a hydrogen atom, a halogen atom, or a radicalthat can be split off by the reaction of the coupler with the oxidizedproduct of an aromatic primary amine-type color developing agent.
 4. Thelight-sensitive material of claim 3, wherein the alkylene radicalrepresented by R₉ has carbon atoms of 1-12.
 5. The light-sensitivematerial of claim 3, wherein X represents --O--, --S--, --SO-- or --SO₂--.
 6. The light-sensitive material of claim 3, wherein Z₃ represents achlorine atom or a fluorine atom.
 7. The light-sensitive material ofclaim 3, wherein R₇ represents a phenyl radical substituted by analkyl-sulfonamide or aryl-sulfonamide radical, alkyl-sulfamoyl, oraryl-sulfamoyl.
 8. The light-sensitive material of claim 3, wherein R₈represents a phenyl radical substituted by an alkyl-sulfonamide oraryl-sulfonamide radical, alkyl-sulfamoyl or aryl-sulfamoyl.
 9. Thelight-sensitive material of claim 3, wherein R₉ represents a pentafluoro phenyl radical.
 10. The silver halide photographiclight-sensitive material of claim 1, wherein the cyan couplers havingthe Formula [II] are the compounds having the following Formula [IV]:##STR17## wherein R₁₁ and R₁₂ may be either the same or different fromeach other and each is a hydrogen atom, an alkyl radical or an alkoxyradical, provided that the sum of the carbon atoms of R₁₁ and R₁₂ isfrom 8 to 16; R₁₃ is a hydrogen atom or an alkyl radical; m is aninteger of 0 to 2; and Z₄ is a hydrogen atom, a halogen atom, or aradical that can be split off by the reaction of the coupler with theoxidized product of an aromatic primary amine-type color developingagent.
 11. The light-sensitive material of claim 10, wherein the alkylradicals represented by R₁ and R₁₂ in Formula [IV] are butyl radicals oramyl radicals, respectively.
 12. The light-sensitive material of claim10, wherein the alkyl radical represented by R₁₃ in Formula [IV] is anethyl radical or a butyl radical.
 13. The light-sensitive material ofclaim 10, wherein the halogen atom represented by Z₄ in Formula [IV] isa chlorine atom.
 14. The light-sensitive material of claim 1, whereinthe cyan coupler having Formula [I] out of the total quantity of thecyan couplers being contained in the silver halide emulsion layer isused in a quantity sufficient to account for from 30 to 90 mole percent.15. The light-sensitive material of claim 14, wherein the cyan couplerhaving Formula [I] out of the total quantity of the cyan couplers beingcontained in the silver halide emulsion layer is used in the quantitysufficient to account for from 50 to 90 mole percent.
 16. Thelight-sensitive material of claim 1, wherein the cyan coupler havingFormula [I] and that having Formula [II] are respectively contained inthe quantity within the range of from 0.1 to 1 mole thereof per mole ofsilver halide.
 17. The light-sensitive material of claim 1, wherein thesupport has thereon a cyan dye image-formable component unit consistingof at least one red-sensitive silver halide emulsion layer containing incombination a cyan coupler having Formula [I] and a cyan coupler havingFormula [II] of claim 1; a magenta dye image-formable component unitconsisting of at least one green-sensitive halide emulsion layercontaining at least one magenta dye forming coupler; and a yellow dyeimage-formable component unit consisting of at least one blue-sensitivesilver halide emulsion layer containing at least one yellow dye formingcoupler.
 18. The light-sensitive material of claim 17, wherein theyellow dye image forming coupler is a compound having the followingFormula [V]: ##STR18## wherein R₁₄ represents an alkyl radical or anaryl radical R₁₅ represents an aryl radical; and Y represents a hydrogenatom or a radical which can be split off during the course of a colordeveloping reaction.
 19. The light-sensitive material of claim 17,wherein the yellow dye forming coupler is a compound having thefollowing Formula [VI]: ##STR19## wherein R₁₆ is a halogen atom, analkoxy radical or an aryloxy radical; R₁₇, R₁₈ and R₁₉ each is ahydrogen atom, a halogen atom, an alkyl radical, an alkenyl radical, analkoxy radical, an aryl radical, an aryloxy radical, a carbonyl radical,a sulfonyl radical, a carbonyl radical, an alkoxycarbonyl radical, acarbonyl radical, a sulfone radical, a sulfamyl radical, a sulfonamidoradical, an acylamido radical, an ureido radical or an amido radical;and Y is as defined in Formula [V] of claim
 18. 20. The light-sensitivematerial of claim 17, wherein the magenta dye forming coupler is acompound having the following Formula [VII]: ##STR20## wherein Ar is anaryl radical; R₂₀ is a hydrogen atom, a halogen atom, an alkyl radicalor an alkoxy radical; R₂₁ is an alkyl radical, an amido radical, animido radical, an N-alkyl-carbamoyl radical, an N-alkyl-sulfamoylradical, an alkyloxy-carbonyl radical, an acyloxy radical, a sulfonamidoradical, or a urethane radical; Y is as defined in Formula [V] of claim18; and W is --NH--, --NHCO-- wherein the N atom is bonded with thecarbon atom of the pyrazolone nucleus or --NHCONH--.